CN106946734A - A kind of method of high-selectivity oxidation benzylamine green syt N benzylidenebutyramides - Google Patents
A kind of method of high-selectivity oxidation benzylamine green syt N benzylidenebutyramides Download PDFInfo
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- CN106946734A CN106946734A CN201710090604.3A CN201710090604A CN106946734A CN 106946734 A CN106946734 A CN 106946734A CN 201710090604 A CN201710090604 A CN 201710090604A CN 106946734 A CN106946734 A CN 106946734A
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- Prior art keywords
- tungstate
- benzylamine
- benzylidenebutyramides
- bismuth
- cadmium
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- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 230000003647 oxidation Effects 0.000 title claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 16
- XQJLGXMAEVIFDR-UHFFFAOYSA-N 2-benzylidenebutanamide Chemical class CCC(C(N)=O)=CC1=CC=CC=C1 XQJLGXMAEVIFDR-UHFFFAOYSA-N 0.000 title abstract 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 35
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 30
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 238000002425 crystallisation Methods 0.000 claims abstract description 25
- 230000008025 crystallization Effects 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000011941 photocatalyst Substances 0.000 claims abstract description 22
- 238000005286 illumination Methods 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- WYSRMZBCJRNZKB-UHFFFAOYSA-N N-benzylidenebutanamide Chemical class C(C1=CC=CC=C1)=NC(CCC)=O WYSRMZBCJRNZKB-UHFFFAOYSA-N 0.000 claims description 16
- 238000010189 synthetic method Methods 0.000 claims description 9
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 32
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 12
- 229910001882 dioxygen Inorganic materials 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- MRZDCFAGABOHQQ-UHFFFAOYSA-N chromium(3+);dioxido(dioxo)tungsten Chemical compound [Cr+3].[Cr+3].[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O MRZDCFAGABOHQQ-UHFFFAOYSA-N 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000004445 quantitative analysis Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000003939 benzylamines Chemical class 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000004451 qualitative analysis Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Chemical class [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 208000019155 Radiation injury Diseases 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000003782 beta lactam antibiotic agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229940035637 spectrum-4 Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002132 β-lactam antibiotic Substances 0.000 description 1
- 229940124586 β-lactam antibiotics Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B01J35/39—
Abstract
The invention provides a kind of method of high-selectivity oxidation benzylamine green syt N benzylidenebutyramides.This method includes：Take cadmium tungstate, bismuth tungstate to be dissolved in alcoholic solution, be uniformly mixed；By mixed solution crystallization, cadmium tungstate bismuth tungstate composite photocatalyst is made through cooling, filtering, separation, drying and other steps after；Take cadmium tungstate bismuth tungstate composite photocatalyst to be dispersed in benzylamine, be passed through oxygen, illumination produces N benzylidenebutyramides.The present invention can improve the conversion ratio of benzylamine by controlling the ratio of catalyst, and obtained N benzylidenebutyramides are selectively more than 99%.The features such as present invention has green, solvent-free, efficient, low energy consumption, and synthesis technique is simple.
Description
【Technical field】
The present invention relates to photochemical catalytic oxidation field, and in particular to a kind of high-selectivity oxidation benzylamine green syt N- benzyl alkene fourths
The method of amine.
【Background technology】
Imines is important intermediate in organic synthesis, has important application in biomedicine field.Due to electrophilic
Property double bond, with other reagents important reaction can occur for imines.N- benzylidenebutyramides can be used for synthesis to have bioactivity as one kind
Natural products and drug candidate important chemical industry product, it can occur addition reaction with ester, acyl chlorides, ketenes etc. can generate β-interior
Acid amides, and the extensive use of beta-lactam antibiotic makes the oxidative synthesis N- benzylidenebutyramides of benzylamine significant.Tradition
Synthetic method formed using primary amine with condensation.The method needs thermal dehydration device, and operation is cumbersome, and a lot
Raw material is difficult to prepare.In recent years, oxidation benzylamine, which prepares N- benzylidenebutyramides, turns into a kind of effective ways, especially under catalytic condition
The green oxidation synthetic method carried out with oxygen, hydrogen peroxide etc. is received significant attention.
The technique that current oxidizing process prepares N- benzylidenebutyramides mainly includes the dehydrogenation of metal catalytic, microwave method, HgO-I2Oxygen
Change etc..But existing method for oxidation remains some defects：Higher reaction temperature, longer reaction time, reaction
Or use substantial amounts of organic solvent in post processing.In recent years, photocatalytic oxidation was originated by the use of solar energy as energy, with molecule
Oxygen realizes organic matter selective oxidation process under room temperature or lower temperature, enjoys the concern of researchers as oxidant.
So far, the heterogeneous catalyst aoxidized for benzylamine mainly has TiO2With with TiO2Based on modified light catalyst, WS2、
Au/SrTiO3、Nb2O5And the novel photocatalyst g-C developed recently3N4.But, there is photocatalytic activity in these photochemical catalysts
Low, visible light-responded weak the shortcomings of.Therefore, a kind of efficiency light is developed to urge agent to realize high-selectivity oxidation benzylamine green syt N-
Benzylidenebutyramide is extremely important and urgent.
Bismuth tungstate (Bi2WO6) it is a kind of cheap, stable and nontoxic pigment, its energy gap is about 2.7eV, with stronger
Visible absorption ability, be applied to the fields such as photocatalysis organic matter degradation, photocatalytic water and organic synthesis.Cadmium tungstate
(CdWO4) belonging to monoclinic system crystal, its energy gap is about 2.7eV, and it has the high and low radiation injury of refractive index, hair
The advantages of luminous intensity is greatly with excellent scintillation properties.
By using the advantage of bismuth tungstate and cadmium tungstate, can develop with visible light-responded, mild oxidation ability, compared with
The catalysis material of the advantages of high visible light catalytic activity, caused industry future realize N- benzylidenebutyramides photocatalytic synthesis into it is strong
Strong concern.
【The content of the invention】
The purpose of the present invention is a kind of method that high selectivity catalysis oxidation benzylamine synthesizes N- benzylidenebutyramides, and this method is high
It is effect, low energy consumption, pollution-free.
The step of present invention prepares effective catalyst is as follows：
Take cadmium tungstate, bismuth tungstate to be dissolved in alcoholic solution, be uniformly mixed；
It is multiple through cooling, filtering, separation, the obtained cadmium tungstate-bismuth tungstate of drying and other steps after by mixed solution crystallization
Closing light catalyst；
Take cadmium tungstate-bismuth tungstate composite photocatalyst to be dispersed in benzylamine, be passed through oxygen, illumination produces N- benzylidenebutyramides.
The cadmium tungstate, bismuth tungstate can both be purchased from it is commercially available, also can now-making-now-using.
Preferably, the cadmium tungstate, bismuth tungstate mixed solution, the wherein concentration of tungstate radicle are 1~50mmol/l.
Preferably, the crystallization temperature is 100~200 DEG C, and crystallization time is 10~48h.
Preferably, the alcoholic solution is ethanol, ethylene glycol or three ethanol solutions.
Preferably, based on the gross mass of reactant, the speed for being passed through oxygen is 20~400mL/min/g.
Preferably, the light irradiation time is 1~24h.
Preferably, the light source of the illumination is xenon lamp, and filters out the light that wavelength is less than 400 nanometers.
Preferably, the mol ratio in the cadmium tungstate-bismuth tungstate composite photocatalyst between cadmium tungstate and bismuth tungstate is 1：
[1~10].
The present invention can prepare CdWO by changing the mol ratio of cadmium and bismuth4-Bi2WO6Composite photo-catalyst, for height
Selective catalytic oxidation benzylamine synthesizes N- benzylidenebutyramides, with efficient, green, energy consumption is small, corrosion-free equipment the features such as, benzylamine turns
The selectivity that rate is more than 10%, N- benzylidenebutyramides is more than 99%.
【Embodiment】
With reference to the embodiment of the present invention, the present invention will be further described；In the following example, cadmium tungstate, bismuth tungstate are equal
For now-making-now-using, directly there is same effect using commercially available cadmium tungstate, bismuth tungstate and following embodiments, and not to the present invention
Technical scheme bring substantial effect.
Embodiment 1
The present invention prepares light with the different mol ratio of chromium tungstate in cadmium tungstate-bismuth tungstate composite photocatalyst, bismuth tungstate and urged
Agent：
The preparation of cadmium tungstate：1.234g cadmium nitrates are taken to be dissolved in 40ml deionized waters and mixed with 0.240g ethylenediamine solutions
Close, stir to form solution A；Sodium tungstate is dissolved in 40ml water and obtains solution B；AB is mixed into 10min, solution is obtained
C；Then by the solution C of gained in 180 DEG C of crystallization 20 hours.Crystallization liquid is separated through cold filtration, be washed with deionized three times,
Absolute ethanol washing once, cadmium tungstate can be obtained in 6 hours in 80 DEG C of dryings；
The preparation of composite：Take 0.041g sodium tungstates to be dissolved in 10ml ethylene glycol solutions, stir to form solution D；
Take 0.121g bismuth nitrates to be dissolved in 10ml ethylene glycol solutions, stir to form solution E；DE is mixed into 10min, obtains molten
Liquid F；Then 0.036g cadmium tungstates are added in F solution, and add 60ml ethanol in wherein mixing 10min formation solution
G, by the solution G of gained in 160 DEG C of crystallization 24 hours.Crystallization liquid is separated through cold filtration, is washed with deionized three times, anhydrous
Ethanol washed once, and 80 DEG C of dryings can obtain composite photo-catalyst in 6 hours.
Using under visible ray, molecular oxygen as oxidizer catalytic oxidation benzylamine prepare N- benzylamine butylene investigated as model reaction
The photocatalytic activity of prepared catalyst：
The composite photocatalyst material prepared by 50 milligrams is taken, 10mmol benzylamines are then added, it is 60mL/ to control oxygen gas flow rate
Min/g, then opens light source (300 watts of xenon lamp adds optical filter and filters the light that wavelength is less than 400 nanometers) illumination 5h, simultaneously
It is room temperature to open condensation water management reacting liquid temperature.Sampled after illumination certain time, catalyst is centrifuged out, then using gas
Phase chromatography-mass spectroscopy is used in conjunction instrument and carries out qualitative analysis to product, using gas chromatograph (GC2010, the detection of hydrogen flameionization device
Device, Shimadzu Corporation's production) quantitative analysis is carried out to product, using biphenyl as internal standard compound during quantitative analysis, benzylamine catalysis oxidation is obtained
The product arrived is N- benzylidenebutyramides.
Embodiment 2~5
Cadmium tungstate, bismuth tungstate composite photocatalyst to different mol ratio, operating procedure and embodiment 1 are similar, only change
The amount that the sodium tungstate of change composite material is added with bismuth nitrate, remaining condition is constant, and is Cat 2, Cat 3, Cat sample number into spectrum
4、Cat 5.Composite catalyst condition and reaction result prepared by embodiment 1~5 is shown in Table 1.
The composite photo-catalyst preparation condition and reaction result of the different mol ratio of table 1
Cadmium tungstate-bismuth tungstate of this ratio of Cat 4 is found by table 1 so that benzylamine conversion ratio is 38.7%, N- benzyl alkene fourths
The selectivity of amine is more than 99%, with optimal photocatalysis effect.
Embodiment 6~10
It is 1 according to the optimal mol ratio of chromium tungstate, bismuth tungstate effect in reactant mixture:7.5 step of embodiment 4, its
Remaining condition is constant, change composite photo-catalyst prepare crystallization temperature, be respectively adopted 100 DEG C, 120 DEG C, 140 DEG C, 180 DEG C, 200
DEG C crystallization 24h, it is T 1, T 2, T 3, T 4, T 5 that its sample, which is compiled, respectively, and remaining operating procedure is similar to Example 4.Implement
Composite catalyst condition and reaction result prepared by example 6~10 is shown in Table 2.
The chromium tungstate of table 2, the mol ratio of bismuth tungstate are 1:7.5 different crystallization temperature conditions and reaction result
Found to obtain different benzylamine conversion ratios under different crystallization temperatures by table 2, wherein the temperature and the phase of embodiment 4
It is optimal crystallization temperature that contrast, which finds 160 degree,.
Embodiment 11~13
It is 1 according to the optimal mol ratio of chromium tungstate, bismuth tungstate effect in reactant mixture:7.5 step of embodiment 4, changes
Become crystallization time prepared by composite photo-catalyst, respectively 12h, 36h, 48h.And its sample compile be H1, H 2, H3, remaining
Condition is constant.Reaction condition is same as Example 4, the composite photo-catalyst preparation condition of the different mol ratio of embodiment 11~13 and
Reaction result is shown in Table 3.
The composite photo-catalyst preparation condition and reaction result of the different mol ratio of table 3
Found to obtain different benzylamine conversion ratios under different crystallization times by table 3, wherein the temperature and the phase of embodiment 4
Contrast finds that 24h is optimal crystallization time.
Embodiment 14~18
Mol ratio according to chromium tungstate, bismuth tungstate is 1:7.5 composite optimal effectiveness are catalyst, probe into it and react bar
Influence of the change of part to its photochemical catalytic oxidation.Exemplified by controlling the different flow velocity of oxygen, be respectively adopted 20mL/min/g,
120mL/min/g, 240mL/min/g, 360mL/min/g and 400mL/min/g oxygen gas flow rate, be designated as accordingly V1, V2,
V3, V4, V5, remaining reaction conditioned response condition are same as Example 4, obtain corresponding reaction result and are shown in Table 4.
The chromium tungstate of table 4, the mol ratio of bismuth tungstate are 1:Different oxygen gas flow rates and reaction result under the conditions of 7.5
It is 1 by the mol ratio of the chromium tungstate of table 4, bismuth tungstate:The reaction result of different oxygen gas flow rates under the conditions of 7.5, finding should
Catalyst is optimal for 60mL/min/g reaction effect in flow velocity.
Embodiment 19~22
Mol ratio according to chromium tungstate, bismuth tungstate is 1:7.5 composite optimal effectiveness are catalyst, when probing into its illumination
Between influence of the change to its photochemical catalytic oxidation.Light application time is respectively adopted for 1h, 10h, 15h, 24, be designated as respectively L1, L2,
L3, L4.Remaining reaction conditioned response condition is same as Example 4, obtains corresponding reaction result and is shown in Table 5.
The chromium tungstate of table 5, the mol ratio of bismuth tungstate are 1:Different light application times and reaction result under the conditions of 7.5
It is 1 by the mol ratio of the chromium tungstate of table 5, bismuth tungstate:The reaction result of different light application times under the conditions of 7.5, finding should
Catalyst is being raised in growth conversion ratio over time, but most fast in reaction 5h speed.The catalyst is finally given to exist
Light application time most preferably 5h.
Comparative example 1
The preparation method of cadmium tungstate：Take 1.234g cadmium nitrates be dissolved in 40ml deionized waters and with 0.240g ethylenediamine solutions
Mixing, stirs to form solution A；Sodium tungstate is dissolved in 40ml water and obtains solution B；AB is mixed into 10min, obtains molten
Liquid C；Then by the solution C of gained in 180 DEG C of crystallization 20 hours.Crystallization liquid is separated through cold filtration, is washed with deionized three
Once, 80 DEG C of dryings can obtain cadmium tungstate in 6 hours to secondary, absolute ethanol washing.
Using under visible ray, molecular oxygen as oxidizer catalytic oxidation benzylamine prepare N- benzylamine butylene investigated as model reaction
The photocatalytic activity of prepared catalyst：The composite photocatalyst material prepared by 50 milligrams is taken, 10mmol benzylamines, control is then added
Oxygen gas flow rate processed is 60mL/min/g, and then opening light source, (300 watts of xenon lamp adds optical filter and filters wavelength less than 400 nanometers
Light) illumination 5h, while it is room temperature to open condensation water management reacting liquid temperature.Sampled after illumination certain time, centrifugation is isolated
Then catalyst is used in conjunction instrument to product progress qualitative analysis using gas chromatography-mass spectrum, using gas chromatograph (GC2010, hydrogen
Flame ion device detector, Shimadzu Corporation's production) quantitative analysis is carried out to product, internal standard is used as using biphenyl during quantitative analysis
Thing.Benzylamine conversion ratio is more than 99% for the selectivity of 2.3%, N- benzylidenebutyramides.
Comparative example 2
The preparation method of bismuth tungstate：Take 0.247g sodium tungstates to be dissolved in 10ml ethylene glycol solutions, stir to form solution
A；Take 0.679g bismuth nitrates to be dissolved in 10ml ethylene glycol solutions, stir to form solution B；AB is mixed into 10min, obtained
Solution C；And add 60ml ethanol in wherein stirring formed solution D stirring 10min, then by the solution D of gained in 160 DEG C of crystallization
24 hours.Crystallization liquid is separated through cold filtration, be washed with deionized three times, absolute ethanol washing once, 80 DEG C of dryings 6 hours
Composite photo-catalyst can be obtained.
Using under visible ray, molecular oxygen as oxidizer catalytic oxidation benzylamine prepare N- benzylamine butylene investigated as model reaction
The photocatalytic activity of prepared catalyst：The composite photocatalyst material prepared by 50 milligrams is taken, 10mmol benzylamines, control is then added
Oxygen gas flow rate processed is 60mL/min/g, and then opening light source, (300 watts of xenon lamp adds optical filter and filters wavelength less than 400 nanometers
Light) illumination 5h, while it is room temperature to open condensation water management reacting liquid temperature.Sampled after illumination certain time, centrifugation is isolated
Then catalyst is used in conjunction instrument to product progress qualitative analysis using gas chromatography-mass spectrum, using gas chromatograph (GC2010, hydrogen
Flame ion device detector, Shimadzu Corporation's production) quantitative analysis is carried out to product, internal standard is used as using biphenyl during quantitative analysis
Thing.Benzylamine conversion ratio is more than 99% for the selectivity of 12.2%, N- benzylidenebutyramides.
Comparative example 3
Take commercially available cadmium tungstate 0.036g and take 0.523g bismuth tungstates to be dissolved in respectively in 10ml ethylene glycol solutions, stir
Form solution A；10min formation solution Bs are mixed after to be dissolved；And add 60ml ethanol and form solution C in wherein stirring and stir
10min is mixed, then by the solution C of gained in 160 DEG C of crystallization 24 hours.Crystallization liquid is separated through cold filtration, is washed with deionized water
Wash three times, absolute ethanol washing once, 80 DEG C of dryings can obtain composite photo-catalyst in 6 hours.
Using under visible ray, molecular oxygen as oxidizer catalytic oxidation benzylamine prepare N- benzylamine butylene investigated as model reaction
The photocatalytic activity of prepared catalyst：The composite photocatalyst material prepared by 50 milligrams is taken, 10mmol benzylamines, control is then added
Oxygen gas flow rate processed is 60mL/min/g, and then opening light source, (300 watts of xenon lamp adds optical filter and filters wavelength less than 400 nanometers
Light) illumination 5h, while it is room temperature to open condensation water management reacting liquid temperature.Sample, centrifuge out after illumination certain time
Then catalyst is used in conjunction instrument to product progress qualitative analysis using gas chromatography-mass spectrum, using gas chromatograph (GC2010, hydrogen
Flame ion device detector, Shimadzu Corporation's production) quantitative analysis is carried out to product, internal standard is used as using biphenyl during quantitative analysis
Thing.Benzylamine conversion ratio is more than 99% for the selectivity of 10.2%, N- benzylidenebutyramides.
The photochemical catalyst photochemical catalytic oxidation benzyl that the inventive method is made compound is can be seen that from above-described embodiment and comparative example
Amine synthesize N- benzylamine butylene, using molecular oxygen as oxidant, at room temperature under visible ray can efficiently, high selectivity preparation N- benzylamines
Butylene is more compared has more preferable activity with commercially available catalyst.
Claims (8)
1. a kind of method of high-selectivity oxidation benzylamine green syt N- benzylidenebutyramides, is comprised the steps of：
Take cadmium tungstate, bismuth tungstate to be dissolved in alcoholic solution, be uniformly mixed；
By mixed solution crystallization, cadmium tungstate-bismuth tungstate complex light is made through cooling, filtering, separation, drying and other steps after
Catalyst；
Take cadmium tungstate-bismuth tungstate composite photocatalyst to be dispersed in benzylamine, be passed through oxygen, illumination produces N- benzylidenebutyramides.
2. synthetic method according to claim 1, it is characterised in that the cadmium tungstate, wherein bismuth tungstate mixed solution, tungsten
The concentration of acid group is 1~50mmol/l.
3. synthetic method according to claim 1, it is characterised in that the crystallization temperature is 100~200 DEG C, during crystallization
Between be 10~48h.
4. synthetic method according to claim 1, it is characterised in that the alcoholic solution is ethanol, ethylene glycol or three ethanol
Solution.
5. synthetic method according to claim 1, it is characterised in that based on the gross mass of reactant, described to be passed through oxygen
Speed be 20~400mL/min/g.
6. synthetic method according to claim 1, it is characterised in that the light irradiation time is 1~24h.
7. synthetic method according to claim 1, it is characterised in that the light source of the illumination is xenon lamp, and filters falling ripple
The long light less than 400 nanometers.
8. synthetic method according to claim 1, it is characterised in that in the cadmium tungstate-bismuth tungstate composite photocatalyst
Mol ratio between cadmium tungstate and bismuth tungstate is 1：[1~10].
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